CN114592228A - Magnesium alloy surface treatment method with uniform and high absorption of visible light - Google Patents
Magnesium alloy surface treatment method with uniform and high absorption of visible light Download PDFInfo
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- CN114592228A CN114592228A CN202210241865.1A CN202210241865A CN114592228A CN 114592228 A CN114592228 A CN 114592228A CN 202210241865 A CN202210241865 A CN 202210241865A CN 114592228 A CN114592228 A CN 114592228A
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- visible light
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000032900 absorption of visible light Effects 0.000 title claims abstract description 15
- 238000004381 surface treatment Methods 0.000 title claims abstract description 12
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 77
- 239000003792 electrolyte Substances 0.000 claims abstract description 64
- 239000000919 ceramic Substances 0.000 claims abstract description 53
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005238 degreasing Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004040 coloring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229940048084 pyrophosphate Drugs 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 235000019263 trisodium citrate Nutrition 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 13
- 229910000733 Li alloy Inorganic materials 0.000 description 21
- 239000001989 lithium alloy Substances 0.000 description 21
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 21
- 230000031700 light absorption Effects 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229960002413 ferric citrate Drugs 0.000 description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- -1 10g/L Chemical compound 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 241000143243 Idaea flaveolaria Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The invention discloses a magnesium alloy surface treatment method with uniform and high absorption of visible light, which is implemented according to the following specific method: step 1, performing surface pretreatment on magnesium alloy; step 2, performing micro-arc oxidation treatment on the pretreated magnesium alloy in a mixed electrolyte system; and 3, post-treating the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2 to prepare a complex-phase black ceramic layer based on the doped MgO, so that the black ceramic layer prepared by adopting a micro-arc oxidation technology can achieve high-proportion uniform absorption in a visible light wave band.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy surface treatment, and relates to a magnesium alloy surface treatment method with uniform and high absorption of visible light wave bands.
Background
With the development of science and technology, diversified optical instruments are widely applied to the fields of astronomy, traffic, medicine and the like, magnesium alloy is used as the lightest metal structural material and can further reduce the dead weight of the instruments when being applied to the field of the optical instruments, but the magnesium alloy is extremely easy to corrode and needs to be subjected to anticorrosion treatment, and in addition, as an optical system generally needs to utilize a high-absorption coating to inhibit the interference of stray light on the imaging of the instruments, the imaging precision is improved, the optical system is required to have high light absorption performance, the reliability of the instruments is improved, meanwhile, the optical instrument has good corrosion resistance, and the surface blackening can improve the absorption rate of the magnesium alloy to visible light.
The micro-arc oxidation technology is a common method in magnesium alloy surface treatment technologies, compared with other surface treatment technologies, the micro-arc oxidation technology is simple and convenient to operate, high in production efficiency and capable of achieving one-step coloring, a micro-arc oxidation ceramic layer is well combined with a substrate, the light aging resistance is excellent, and the corrosion prevention and coloring requirements can be met at the same time, but the magnesium alloy black film layer prepared by the micro-arc oxidation technology can achieve 95% of high absorption rate in a visible light wave band, but the absorption curve cannot achieve uniform high absorption in an orange red light wave band in a descending trend, and cannot meet the requirement that the light absorption rate of a high-precision instrument is larger than 97%.
Disclosure of Invention
The invention aims to provide a magnesium alloy surface treatment method with uniform and high absorption of visible light wave bands, which utilizes the principle that different objects have different light absorption wave bands to prepare a multi-phase ceramic layer which takes doped magnesium oxide as a base and mainly absorbs a second phase more than a red-orange light wave band; the method solves the problems that the absorption performance of the MgO-based black ceramic layer prepared by doping coloring salt in the micro-arc oxidation technology is reduced in orange red wave bands, the average absorption rate is limited, the uniform absorption rate of visible light in different wave bands is improved, and the full-wave band high-uniform absorption of the visible light is achieved.
The technical scheme adopted by the invention is that the magnesium alloy surface treatment method with uniform and high absorption of visible light wave band is implemented according to the following steps:
step 1, performing surface pretreatment on magnesium alloy;
step 2, performing micro-arc oxidation treatment on the pretreated magnesium alloy in a mixed electrolyte system;
and 3, post-treating the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2.
The invention is also characterized in that:
wherein the pretreatment in the step 1 specifically comprises the following steps: sequentially polishing magnesium alloy plates on a metallographic sample pre-polishing machine by using abrasive paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium alloys, firstly washing the surfaces by using deionized water, then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol, drying and weighing the cleaned surfaces to obtain the pretreated magnesium alloys;
wherein the step 2 is implemented according to the following steps:
step 2.1, preparing mixed electrolyte, and placing the magnesium alloy treated in the step 1 into the mixed electrolyte;
step 2.2, performing micro-arc oxidation on the magnesium alloy in the step 2.1, continuously introducing compressed air into the mixed electrolyte in the micro-arc oxidation process, wherein the temperature of the electrolyte is not higher than 30 ℃, after the oxidation treatment, cleaning the magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling to obtain a magnesium alloy micro-arc oxidation black ceramic layer;
wherein the power supply mode of the micro-arc oxidation in the step 2.2 is a constant voltage power supply mode, and the electrical parameters are as follows: the positive voltage is 350-600V, the negative voltage is 0-100V, the positive frequency is 800-3000 Hz, the negative frequency is 200-2000 Hz, the positive duty ratio is 10-30%, the negative duty ratio is 5-15%, the positive progression is 0-20, the negative progression is 0-10, and the oxidation time is 5-30 min;
the composite electrolyte system comprises a main film forming agent, an auxiliary film forming agent, a coloring salt, a complexing agent and deionized water, wherein the concentration of the electrolyte is 10-60 g/L, and the pH value of the mixed electrolyte system is 11-14;
wherein the main film-forming agent is one or two mixtures of phosphate, silicate and carbonate, the auxiliary film-forming agent is one or more mixtures of potassium hydroxide, sodium hydroxide, potassium fluoride, sodium fluoride and sodium metaaluminate, the coloring salt is one or more mixtures of metavanadate, tungstate, ferric salt and copper salt, and the complexing agent is one or more mixtures of EDTA, EDTA-2Na, potassium sodium tartrate, trisodium citrate and pyrophosphate;
and 3, specifically, degreasing and deoiling the surface of the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, drying and weighing after cleaning is finished, and thus obtaining the magnesium alloy micro-arc oxidation black uniform high-absorption coating.
The invention is also characterized in that: the black ceramic layer with uniform and high absorption of visible light is prepared by selecting the composite coloring salt, utilizing different wavelength absorption properties of substances at different wave bands and adopting the micro-arc oxidation technology.
The invention has the beneficial effects that:
the invention relates to a magnesium alloy surface treatment method with uniform and high absorption of visible light, which solves the problems that a single-phase MgO-based black ceramic layer prepared by doping coloring salt by adopting a micro-arc oxidation technology has non-uniform absorption rate on the wavelengths of different wave bands in a visible light range, so that the average absorption rate is limited and cannot reach uniform and high absorption. Compared with the prior art, the method has the following advantages:
by utilizing the micro-arc oxidation technology, coloring ions in the electrolyte are adsorbed to the surface of a sample to participate in reaction, the content of the coloring ions doped in the ceramic layer can be controlled by adjusting electrical parameters, a composite coloring salt is selected by utilizing the absorption principle of a semiconductor material to different wave bands, the forbidden bandwidth of MgO is reduced to a visible light wave band, a new iron oxide phase is formed by doping excessive iron salt under the action of micro-arc oxidation, the formed ceramic layer is of a complex phase structure, the problem of low absorption rate of the single phase structure to a red and orange light wave band is solved, the electronic transition can be realized by the small energy of the red and orange wave band, the high-proportion uniform absorption black ceramic layer with the absorption rate of visible light reaching more than 97 percent is prepared in one step, meanwhile, the ceramic layer prepared on the magnesium alloy by adopting the micro-arc oxidation technology has small weight, and the corrosion prevention-coloring requirements are met.
Drawings
FIG. 1 is a light absorption curve of a black ceramic layer on the surface of AZ31 magnesium alloy prepared in example 1 of the present invention;
fig. 2 is a graph showing the light absorption of a black ceramic layer on the surface of LA103Z magnesium lithium alloy prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a magnesium alloy surface treatment method with uniform and high absorption of visible light, which is implemented by the following steps:
step 1, performing surface pretreatment on magnesium alloy;
sequentially polishing magnesium alloy plates on a metallographic sample pre-polishing machine by using abrasive paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium alloys, firstly washing the surfaces by using deionized water, then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol, drying and weighing the cleaned surfaces to obtain the pretreated magnesium alloys;
step 2, performing micro-arc oxidation treatment on the pretreated magnesium alloy in a mixed electrolyte system:
step 2.1, preparing mixed electrolyte, and placing the magnesium alloy treated in the step 1 into a mixed electrolyte system;
the composite electrolyte system comprises a main film forming agent, an auxiliary film forming agent, a coloring salt, a complexing agent and deionized water, wherein the concentration of the electrolyte is 10-60 g/L, and the pH value of the mixed electrolyte system is 11-14;
the main film-forming agent is one or a mixture of two of phosphate, silicate and carbonate, the auxiliary film-forming agent is one or a mixture of more of potassium hydroxide, sodium hydroxide, potassium fluoride, sodium fluoride and sodium metaaluminate, the coloring salt is one or a mixture of more of copper citrate, copper sulfate, copper phosphate, copper pyrophosphate, basic copper carbonate, copper acetate, ferric citrate, ferrous sulfate and ferric acetate, and the complexing agent is one or a mixture of more of EDTA, EDTA-2Na, potassium sodium tartrate, trisodium citrate and pyrophosphate;
step 2.2, performing micro-arc oxidation on the magnesium alloy in the step 2.1, continuously introducing compressed air into the mixed electrolyte in the micro-arc oxidation process, keeping the temperature of the electrolyte not higher than 30 ℃, after oxidation treatment, cleaning the magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling to obtain a magnesium alloy micro-arc oxidation black ceramic layer;
wherein the power supply mode of the micro-arc oxidation in the step 2.2 is a constant voltage power supply mode, and the electrical parameters are as follows: the positive voltage is 350-600V, the negative voltage is 0-100V, the positive frequency is 800-3000 Hz, the negative frequency is 200-2000 Hz, the positive duty ratio is 10-30%, the negative duty ratio is 5-15%, the positive progression is 0-20, the negative progression is 0-10, and the oxidation time is 5-30 min;
and 3, post-treating the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2:
and (3) degreasing and deoiling the surface of the magnesium alloy micro-arc oxidation ceramic layer obtained in the step (2), cleaning the electrolyte attached to the surface of the coating, washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, drying and weighing with a blower after cleaning is finished, and thus obtaining the magnesium alloy micro-arc oxidation uniform high-absorption coating.
The method of the invention utilizes micro-arc oxidation technology, takes magnesium alloy as an anode, stainless steel sheets as a cathode, adopts copper salt and iron salt co-doping, and Cu is adopted according to the principle of homogeneous homography2+、Fe2+The ceramic layer is a complex phase structure which makes up the problem that a single-phase MgO-based ceramic layer has low absorption rate on red and orange light wave bands, coloring ions are doped to provide more electrons and holes for the ceramic layer, impurity energy levels are introduced, the forbidden bandwidth of the ceramic layer is adjusted to be less than 1.7ev, and the high-proportion uniform absorption black series ceramic layer with the absorption rate of visible light reaching more than 97% is prepared in one step.
Example 1
Step 1, performing surface pretreatment on AZ31 magnesium alloy:
sequentially polishing AZ31 magnesium alloy plates on a metallographic specimen pre-polishing machine by using sand paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium alloys, firstly washing the surfaces by using deionized water, and then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol to obtain the pretreated magnesium alloys;
step 2, preparing electrolyte with pH of 13, wherein the electrolyte comprises 10g/L of sodium silicate, 8g/L of potassium fluoride, 10g/L, EDTA 2g/L of potassium hydroxide, 15g/L of copper sulfate, 15g/L of ferric citrate and the balance of deionized water; placing the AZ31 magnesium alloy treated in the step 1 into electrolyte, taking a stainless steel sheet as a cathode and an AZ31 magnesium alloy as an anode; setting the positive frequency of 1200Hz, the negative frequency of 500Hz, the positive energy level of 12, the negative energy level of 3, the positive voltage of 450V, the negative voltage of 40V and the micro-arc oxidation time of 15min, continuously introducing compressed air into the electrolyte during the micro-arc oxidation process for stirring in order to reduce the concentration polarization and temperature nonuniformity of the electrolyte, and keeping the temperature of the electrolyte not higher than 30 ℃; after micro-arc oxidation is finished, cleaning an AZ31 magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling;
and 3, degreasing and deoiling the surface of the AZ31 magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, and drying with a blower after cleaning to obtain the AZ31 magnesium alloy micro-arc oxidation black coating.
Testing the light absorption performance of the surface of the black ceramic layer on the surface of the AZ31 magnesium alloy, wherein the scanning interval is 300-800 nm, the scanning speed is 300nm/min, and the result is shown in figure 1; the wavelength range of visible light is in the double vertical lines in the graph, the light absorption rate in the range of 380 nm-780 nm is as high as 97.9%, the visible light band is uniformly absorbed in a high proportion, and the descending trend does not occur. The color value of the black micro-arc oxidation treated sample was 20, and the thickness was 14.5. mu.m.
Example 2
Step 1, performing surface pretreatment on LA103Z magnesium-lithium alloy:
sequentially polishing LA103Z magnesium-lithium alloy plates on a metallographic sample pre-grinding machine by using sand paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium-lithium alloy plates, firstly washing the surfaces by using deionized water, and then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol to obtain the pretreated magnesium-lithium alloy;
and 2, preparing an electrolyte with the pH value of 13, wherein the electrolyte comprises EDTA-2Na 0.5g/L, potassium sodium tartrate 10g/L, copper phosphate 14g/L, ferrous sulfate 14g/L, sodium metaaluminate 4g/L, sodium hexametaphosphate 8g/L, sodium fluoride 8g/L, potassium hydroxide 14g/L and the balance of deionized water. And (3) placing the magnesium-lithium alloy treated in the step (1) into electrolyte, taking a stainless steel sheet as a cathode, and taking the magnesium-lithium alloy as an anode. Setting the positive frequency of 1200Hz, the negative frequency of 500Hz, the positive energy level of 12, the negative energy level of 3, the positive voltage of 450V, the negative voltage of 80V and the micro-arc oxidation time of 15min, continuously introducing compressed air into the electrolyte during the micro-arc oxidation process for stirring in order to reduce the concentration polarization and temperature nonuniformity of the electrolyte, and keeping the temperature of the electrolyte not higher than 30 ℃; and after the micro-arc oxidation is finished, cleaning the magnesium-lithium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling.
Step 3, degreasing and deoiling the surface of the magnesium-lithium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, and drying with a blower after cleaning to obtain a magnesium-lithium alloy micro-arc oxidation black coating;
performing a light absorption performance test on the surface of the prepared black ceramic layer on the surface of the LA103Z magnesium-lithium alloy, wherein the scanning interval is 300-800 nm, the scanning speed is 300nm/min, and the result is shown in FIG. 2; in the figure, the wavelength range of visible light is within the double vertical lines, the light absorption rate within the range of 380 nm-780 nm is 97%, the visible light wave band is uniformly absorbed in a high proportion, and the trend of decline does not appear. The color value of the black micro-arc oxidation treated sample was 20.3 and the thickness was 13 μm.
Example 3
Step 1, performing surface pretreatment on AZ31 magnesium alloy:
and (2) sequentially polishing AZ31 magnesium alloy plates on a metallographic specimen pre-polishing machine by using sand paper, chamfering the edges, degreasing and deoiling the surfaces of the polished magnesium alloy, washing by using deionized water, and then ultrasonically cleaning for 15min by using absolute ethyl alcohol to obtain the pretreated magnesium alloy.
Step 2, preparing electrolyte with pH of 13, wherein the electrolyte comprises 10g/L of sodium silicate, 8g/L of potassium fluoride, 10g/L, EDTA 2g/L of potassium hydroxide, 15g/L of copper sulfate, 12g/L of ferrous sulfate and the balance of deionized water; placing the AZ31 magnesium alloy treated in the step 1 into electrolyte, taking a stainless steel sheet as a cathode and an AZ31 magnesium alloy as an anode; setting the positive frequency of 1200Hz, the negative frequency of 500Hz, the positive energy level of 12, the negative energy level of 3, the positive voltage of 450V, the negative voltage of 40V and the micro-arc oxidation time of 15min, continuously introducing compressed air into the electrolyte during the micro-arc oxidation process for stirring in order to reduce the concentration polarization and temperature nonuniformity of the electrolyte, and keeping the temperature of the electrolyte not higher than 30 ℃; and after the micro-arc oxidation is finished, cleaning the AZ31 magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling.
And 3, degreasing and deoiling the surface of the AZ31 magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, and drying with a blower after cleaning to obtain the AZ31 magnesium alloy micro-arc oxidation black coating.
And (3) performing light absorption performance test on the surface of the black ceramic layer on the surface of the AZ31 magnesium alloy, wherein the scanning interval is 300-800 nm, the scanning speed is 300nm/min, and the result shows that the absorption rate of the ceramic layer in the visible light range of 380-780 nm is as high as 97.1%, the ceramic layer uniformly absorbs the visible light wave band in a high proportion, the color value of the sample subjected to black micro-arc oxidation treatment is 20.41, and the thickness of the sample is 14 microns.
Example 4
Step 1, performing surface pretreatment on AZ31 magnesium alloy:
sequentially polishing AZ31 magnesium alloy plates on a metallographic specimen pre-polishing machine by using sand paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium alloys, firstly washing the surfaces by using deionized water, and then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol to obtain the pretreated magnesium alloys;
step 2, preparing electrolyte with pH of 13, wherein the electrolyte comprises 6g/L of sodium hexametaphosphate, 8g/L of sodium fluoride, 5g/L of sodium metaaluminate, 10g/L, EDTA 2g/L of potassium hydroxide, 17g/L of copper pyrophosphate, 8g/L of ferric citrate and the balance of deionized water; placing the AZ31 magnesium alloy treated in the step 1 into electrolyte, taking a stainless steel sheet as a cathode and an AZ31 magnesium alloy as an anode; setting the positive frequency of 1200Hz, the negative frequency of 500Hz, the positive energy level of 12, the negative energy level of 3, the positive voltage of 450V, the negative voltage of 40V and the micro-arc oxidation time of 15min, continuously introducing compressed air into the electrolyte during the micro-arc oxidation process for stirring in order to reduce the concentration polarization and temperature nonuniformity of the electrolyte, and keeping the temperature of the electrolyte not higher than 30 ℃; after micro-arc oxidation is finished, cleaning an AZ31 magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling;
step 3, degreasing and deoiling the surface of the AZ31 magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, firstly washing the coating by using deionized water, then ultrasonically cleaning the coating for 15min by using absolute ethyl alcohol, and drying the coating by using a blower after the cleaning is finished to obtain an AZ31 magnesium alloy micro-arc oxidation black coating;
and (3) carrying out light absorption performance test on the surface of the black ceramic layer on the surface of the AZ31 magnesium alloy, wherein the scanning interval is 300-800 nm, and the scanning speed is 300nm/min, and the result shows that the absorption rate of the ceramic layer is 95% in the visible light range of 380-780 nm, and the ceramic layer uniformly absorbs the visible light wave band in a high proportion without a descending trend. The color value of the black micro-arc oxidation treated sample was 20.33, and the thickness was 14 μm.
Example 5
Step 1, performing surface pretreatment on LA103Z magnesium-lithium alloy:
sequentially polishing LA103Z magnesium-lithium alloy plates on a metallographic sample pre-grinding machine by using sand paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium-lithium alloys, firstly washing the surfaces by using deionized water, then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol, and drying and weighing the cleaned surfaces by using a blower to obtain the pretreated magnesium-lithium alloys;
and 2, preparing an electrolyte with the pH value of 13, wherein the electrolyte comprises 0.5g/L of EDTA-2Na, 10g/L of potassium sodium tartrate, 12g/L of copper phosphate, 12g/L of ferric citrate, 10g/L of sodium carbonate, 8g/L of potassium fluoride, 14g/L of potassium hydroxide and the balance of deionized water. And (3) placing the magnesium-lithium alloy treated in the step (1) into an electrolyte, and taking the stainless steel sheet as a cathode and the magnesium-lithium alloy as an anode. Setting the positive frequency of 1200Hz, the negative frequency of 500Hz, the positive energy level of 12, the negative energy level of 3, the positive voltage of 450V, the negative voltage of 70V and the micro-arc oxidation time of 15min, continuously introducing compressed air into the electrolyte during the micro-arc oxidation process for stirring in order to reduce the concentration polarization and temperature nonuniformity of the electrolyte, and keeping the temperature of the electrolyte not higher than 30 ℃; after micro-arc oxidation is finished, cleaning the magnesium-lithium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling;
step 3, degreasing and deoiling the surface of the magnesium-lithium alloy micro-arc oxidation ceramic layer obtained in the step 2, cleaning the electrolyte attached to the surface of the coating, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol for 15min, drying and weighing with a blower after cleaning is finished, and obtaining a magnesium-lithium alloy micro-arc oxidation black coating;
and (3) performing light absorption performance test on the surface of the prepared black ceramic layer on the surface of the LA103Z magnesium-lithium alloy, wherein the scanning interval is 300-800 nm, the scanning speed is 300nm/min, the absorption rate of the ceramic layer in the visible light wavelength range of 380-780 nm is 96.85%, the ceramic layer uniformly absorbs the visible light wave band in a high proportion, and the trend of decline does not occur. The color number of the black micro-arc oxidation treated sample was 20.65 and the thickness was 14 μm.
The weight of the ceramic layer is reduced after micro-arc oxidation treatment of a sample with the size of 3cm multiplied by 0.5cm, the weight gain rate is 2.09 percent, and the weight gain is only 0.1431 g.
Claims (7)
1. A magnesium alloy surface treatment method with uniform and high absorption of visible light is characterized by comprising the following steps:
step 1, performing surface pretreatment on magnesium alloy;
step 2, performing micro-arc oxidation treatment on the pretreated magnesium alloy in a mixed electrolyte system;
and 3, post-treating the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2.
2. The method for treating the surface of the magnesium alloy with uniform and high absorption of visible light according to claim 1, wherein the pretreatment in the step 1 is specifically as follows: the method comprises the steps of sequentially polishing magnesium alloy plates on a metallographic specimen pre-grinding machine by using abrasive paper, chamfering edges, degreasing and deoiling the surfaces of the polished magnesium alloys, firstly washing the surfaces by using deionized water, then ultrasonically cleaning the surfaces for 15min by using absolute ethyl alcohol, drying and weighing the cleaned surfaces to obtain the pretreated magnesium alloys.
3. The method for treating the surface of the magnesium alloy with uniform and high absorption of visible light according to claim 1, wherein the step 2 is specifically carried out according to the following steps:
step 2.1, preparing mixed electrolyte, and placing the magnesium alloy treated in the step 1 into the mixed electrolyte;
and 2.2, performing micro-arc oxidation on the magnesium alloy in the step 2.1, continuously introducing compressed air into the mixed electrolyte in the micro-arc oxidation process, keeping the temperature of the electrolyte not higher than 30 ℃, after the oxidation treatment, cleaning the magnesium alloy micro-arc oxidation ceramic layer in deionized water, drying and cooling to obtain the magnesium alloy micro-arc oxidation ceramic layer.
4. The method for processing the surface of the magnesium alloy with uniform and high absorption of visible light as claimed in claim 3, wherein the power mode of the micro-arc oxidation in the step 2.2 is a constant voltage power mode, and the electrical parameters are as follows: the positive voltage is 350-600V, the negative voltage is 0-100V, the positive frequency is 800-3000 Hz, the negative frequency is 200-2000 Hz, the positive duty ratio is 10-30%, the negative duty ratio is 5-15%, the positive progression is 0-20, the negative progression is 0-10, and the oxidation time is 5-30 min.
5. The method for treating the surface of the magnesium alloy with uniform and high absorption of visible light according to claim 3, wherein the composite electrolyte system comprises a main film-forming agent, an auxiliary film-forming agent, a coloring salt, a complexing agent and deionized water, the concentration of the electrolyte is 10-60 g/L, and the pH value of the mixed electrolyte system is 11-14.
6. The method for processing the surface of the magnesium alloy with uniform and high absorption of the visible light as claimed in claim 5, wherein the primary film-forming agent is one or a mixture of two of phosphate, silicate and carbonate, the auxiliary film-forming agent is one or a mixture of two of potassium hydroxide, sodium hydroxide, potassium fluoride, sodium fluoride and sodium metaaluminate, the coloring salt is one or a mixture of more of metavanadate, tungstate, iron salt and copper salt, and the complexing agent is one or a mixture of more of EDTA, EDTA-2Na, potassium sodium tartrate, trisodium citrate and pyrophosphate.
7. The method for treating the surface of the magnesium alloy with uniform and high absorption of visible light according to claim 1, wherein the step 3 is specifically to perform degreasing and degreasing treatment on the surface of the magnesium alloy micro-arc oxidation ceramic layer obtained in the step 2, clean the electrolyte attached to the surface of the coating, firstly wash the surface with deionized water, then perform ultrasonic cleaning for 15min with absolute ethyl alcohol, dry and weigh the surface after cleaning, and obtain the magnesium alloy micro-arc oxidation black uniform and high absorption coating.
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| 辛童: "基于第一性原理研究镁合金微弧氧化黑色陶瓷层着色元素的选择", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 01, pages 169 - 171 * |
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